Methylol phenol unsaturatep



Patented Dec. 18, 1951 METHYLOL PHENOL UNsa'l-lllltgl lp ETHERS' Robert W, Martin, Lepox, Mass., assignor eral Electric Company, a corporation t -die York No Drawing. Application January Serial No. 204,463

14 Claims. (Cl. 260-6k3) This application is -a continuation-in-part of my earlier filed application, Serial No. 122,128, filed October 18, 1949., and assigned to the same assignee as the present invention.

This invention relatestomethylol phenol others corresponding to the general formula:

- ,mon

where R represents an unsaturated aliphatic group containing at least three carbon atoms,

contain compounds corresponding to general formula where -;R- has --the meaning 1 given above and laz -1s aninteger equal-.to-froml to 2, inclusive.

-The .chemicalcompositions embraced by the instant application-are generally prepared :from pure crystallinemetallic salts of 2,4,6-tris(hy droxymethyl) phenolwherein-the metallic atom substituted for the hydrogen on the phenolic hydrogen group 'is either sodium -or barium. -It

has been found that sodium and bariumsalts of trimethylol phenol may be formed very simply and isolated as crystalline compounds. More particularly, it has been found that crystalline sodium and barium salts of trimethylol phenol may beprepared by efiecting reaction between about three mols ofiormaldehyde and one mol of phenol inthe presence of about one mol of alkali such asthehy-droxides of sodium and barium at a temperature such that no resinous material is formed. This temperature has been found to range up to about 65 C. above which temperature undesired side reactions take place. The salt of trimethylolphenol can then be precipitated by diluting or pouring the reaction mixture into a suitable water-miscible solvent and separated from the liquid. by. filtration, decantation orother suitable means.

While the-exampleabovecalls for molar quan- The halogen tities of alkali, only catalytic quantities of alkali, for example, aboutpr ie er cent by weight, are required for the phenol ornialdehyde reaction. It will he s'eenitrieretore thattphenoland formaldehyde inay allowed .to react to form the thirnethylbl wmpound :in :the .presence ,of .a small amount bf alkali at which -time the rest of the alkali may he added to form :the salt.

Many solvents parelsuitable for precipitating the salts or trimethylolkphenol, e. g., methanol, ethanol, nepropanol, .isopropanol, tertiary butanol, secondary mutanol. lisobutanol, nebutanol. =tertiaryiamylalcohol, iallylalcohol, ,diacetone ,alcohoLbuts'zl carhitol, ipyridine, 2-(2-hydroxy,- ethyl) (pyridine, -.pheny1l'ollosol ve, acetone, ace- .tonitrile'. .propionitril'e. .morpholine, diethylenetriamine, methylal,;di'methyl cellosolve, dioxane, eta material entrants 5 em han 9 ee l n ears a e ch m s mi e ii t mtaing a gents'and particularly those with tfijdbr three carbon atoms flhe preferred precipitating agents are ethanoL'propanol, isopropanol and acetone. .ofithesaiethanqliis-most suitable from the :point of lri eyrgo'f ilqw ,cost. availability and purity of ithemroductiobtained. Mixtures .of ,the above precipitatin agen slals a at ee found JZObgjlfll'yiUSGflll- Amon $1 6 mixt r s -..W .1iCl. are suitable a atby al,u,nie. izllfltn-but n leand methanol ms-fiflmle hanol andacetonelandfill-59 nramyl alcohol ,and methanol;

-f1 he oply-metalthydroxides; fou 0 be s ble for thetpr'epa. salt 0 .4,6,tris yd oxv.- methyl phenqlsto rimeth l l ph ols are sodium and e arium hydro ides- ;While ,formalder hyde is mentioned aboye equiyalent amounts of paraformalg eli yde m ay be used.

h ellows ga new ustra e th preparation of the 'sbdiurr'i and'barium salts 6f trimethylol phenol or 2,4, 6-tris(hydroxymethyl) phenol:

Q PZEM ME- ,l

l hemeticalyiel 3:13.598

Actual fielder-@335 ,pqtaby t reiszlzt or 81. of

,theory autasao 1; teatime It}; To 76.2 parts Wei git (0.94%- 1210i; '0: f ormalin 23.5 parts by weight (0.25 mol) of phenol were" was filtered after standing three or four-hours and washed with acetone and dried.

Theoretical yield5l.5 {parts by weight Actual yield49.4 par t .by weight or 96% of theory I I Example III Formalin in the amount of 140 parts-by weight (1.73 mols), forty-seven parts by weight (0.5 mol) of phenol and forty-seven parts by weight (0.55 equivalents) anhydrous. barium hydroxide dissolved in seventy-five parts by weight of hot water were mixedin that order. .The reaction mixture was kept at a temperature of 30? C. or lower for two hours. The mixture was allowed to react for twenty-four hours at-iroom temperature. Ethanol in the amountiof 1600 parts by weight was added. with vigorous. mechanical stirring. The resulting precipitate,- after standing a few hours, was filtered off, washed with acetone and dried in a vacuum desiccator..

Theoretical yield- 1253 parts by weight Actual yield'-'-97.9 partsby weight'or 77.8% of theory I tem l To 76.2 parts by Weight (0.945 mol) of formalin were added while stirring 235 parts by weight (0.25 mol) of phenol-and twelve parts by weight (0.33 mol) -of sodium-hydroxide,- dissolved in fifteen parts by weight of water. The temperature of the reaction mixture washeld at 30 C. or less for twohours. The-mixture was put in an oven for twenty two hours --at a temperature of 40 C. Next, 804 par-ts by weight of n-propanol was poured into-the--reaction mixture and the mix stirred. The resulting precipitate was filtered off, washed withacetone -and ether and dried in a vacuum desiccator.

Theoretical yield-$1.5 parts. by weight Actual yield-50'.8 part'sby weight or 98% of theory The identity of the sodium 2,4,6-tris(hydroxy:-

methyl) -phenate was 'established by preparing the known derivative 2,4, 6-tris(acetoxymethyl) phenyl acetate. 'More particular details of this identification are found in my earlier application Serial No. 122,128, filed'Qctober '18, 19.50, of which the present application a. continuation-inpart. 1 f' The sodium and barium 2,4','6etris(hydroxymethyl) phenates, described. above are then reacted with other compoun'd's' to provide a class of primary polyhy'd'ric alcohols with afwide'range of applications in the chemical, plastics and coating arts. More particularly, such compounds are the ethers formed by theetherification of the phenolic hydroxyl groups,v and "which form the subject matter of the present application. Such etherification considerably retards the tendency of the tris (hydroxymethyl) -'compound'to resinify and hence makes it available'fora number of other reactions and. applications-not. possible with sodium tris (hydroxymethyl) phenol. --For 4 example, etherification of {the phenolic hydroxyl group greatly improvesthealkali resistance of resinous compositions containing them compared to the same compositions wherein the phenolic group has not been etherified.

The ethers prepared from the sodium and barium 2,4,6-tris(hydroxymethyl) phenates may be represented by the general formula:

HOHzC CHIOH where R has the meaning given above. The following examples illustrate the preparation of various ethers coming within the scope of the above-identified general formula. All parts are by weight.

Example V A mixture of 139 parts sodium 2,4,6-tris(hydroxymethyl) phenate, 126 parts methyl iodide and 440 parts methanol was divided equally between three bottles. The bottles were sealed and placed in an oven at 65 C. for about fifteen to twenty hours. The bottles were cooled and opened. The methanol was boiled off and the products were dissolved in amyl alcohol. The amyl alcohol solution was washed with an aqueous solution of sodium carbonate. The amyl alcohol was distilled off under vacuum. The product, 1-methoxy-2,4,6-tris(hydroxymethyl) benzene was a viscous light brown syrup.

Yield-ll8 parts by weight. Theory=l34 parts by weight Methoxyl content=l5.33%, 15.70%

Theory=15.66%

Example VI In this example, 42 grams sodium trimethylol phenate, 28 grams allyl'bromide, 8 grams K200: and 5 ml. acetone were mixedtogether and refluxed for 12 hours. The solution was filtered to remove any insoluble salts and the acetone was removed under vacuum to give 30 grams of a very light tan liquid. Analysis of this material showed it to be the allyl ether of methylol phenol and to have the following percents hydrogen and carbon, and the physical constants shown below:

Calculated for C12HleO4: C, 64.26%; H. 7.19%.

Found: C, 64.9%; H, 7.0% Density=1.22l; refractive index=l.575

The allyl ether of trimethylol phenol was also prepared by forming a mixture of 42 grams sodium trimethylol phenate, 28 grams allyl bromide, 8 grams K2CO3 and 500 ml. methanol. The mixture was refluxed for about 6 hours and the major portion of solvent removed under a vacuum. The product was then mixed with water and extracted with ether to remove anyunreacted allyl bromide. The aqueous solution was then extracted with amyl alcohol and the latter re? moved from the product by heating at 50-80 C. under a vacuum of 1-2 mm. to give 31 grams of a light brown liquid which had the following physical constants and carbon and hydrogen analyses:

Calculated for C12H16042 C, 64.26%; H, 7.19%.

Found: C, 65.67%; H, 7.20% 1 Density=l.'20; refractive index=l.579

Example V1.11

210' parts sodium 2 ;4, 6 --tris(hydr;o:E-ymethyl*) phenate was added a solution of 130 partsallyl bromide in 4'75 parts methanol, The mixture was refluxed with stirring for two hours. The metlranol was distilled oil under vacuum and amyl alcohol added. The amyl alcohol solution was washed with a solution of saturated-sodium-carbonaterpotassium chloride and was dried over anhydrous sodium sulphate. The arnyl alcohol was removed under vacuum. The product;- 1:- allyloxy-2,4,'6 trisihydroxymethynbenzene, was-a brown syrup. 1

=-1.4. Partsbx wei ht. Theerx=224.

Emample-- VIII samea Example VII except. mature-mixture washeated for. two and one-half to three hours 8.1145 C. (and then-M6 as. two. hours. F a. n m of re ctionsof is examp e. thecom version to the allyl, ether. was found torange romeo per cent to 100. per cent.

Example: IX

' Forty-two. p rt by i ht or he sod um 2.4.6.- trismyd o ymetbyb phenatewas. placedin abet-- tle with forty parts by volume of a 2.5v per, cent. solution of sodium, hydroxide, 26.51 partsv by weight. of. be zyl, chloride was added as. well. as hirty-two parts by weight of methanol. The reaction inglied ents. were, shaken at. 55 C. for forty-eight hours. The cooled contents oi the. bottle. were poured;into 209-3 00 parts by. weight of, hot. water. heated for ten o fif e n minutes nd stirred. When .st r nswas stopped. th med.- uetseparatedout as an. oily layer, Thewashed p o ct was. disso ved. in acetone. filter d. and the water and acetone distilled off. The product. 1, benzyloxy-2,4,6 trisihy'droxymethyl) benzene, was a brown syrup. The theoretical yield was 54,8 parts by weight, the actual yieldwas. 3,8.92 parts by we o .71. per, ce t-y e d- Example X Example XI.-

Example IX was again repeated. using 2313' parts by weight 2,3-dichloropropene-l in lieu of the benzyl chloride.- Methanol was not used; The product, 1 (2' chloroallyloxy)-2,,6 tris(hydroxymethyl) benzene was a viscous brown syrup.

The yield of 44.52'parts by weight was 86 'per cent of the theoretical value of 51.7 parts by weight.

Example. XII

Example IX was repeated using 23.3 parts by weight of 1,3-dichloropropene-1 in place of benzyl chloride and without the use of methanol. The 1-(3-chloroally1oxy)-2,4,6 tris(hydroxymethyl) benzene:ivas...=i v viscous ,broyv-nsyrup. The;

yield was 40.82 parts-by. weightor-IQ centoi; the theoretical value,of-. 51.7 grams.

The la d t rs f tri eth lol phenolsihave esins. 'heiruseinconjunction .with the various ncreas s-r markably th resistance of; the esins. to alkalis. acids,- soap solutions, solvents, in i other; corrosive. chemicals. Theweatherbility andzr sistance to-salt spray isuch treated sinsisal e. reatly-enhanced..

'Theseethers find. use in. low shrinkage castin es ns: and in molding: and putting compoun areyuseful. also: inlaminatins e ins and in the: production of; films. varnishes. wire coatings. The. low; watch absorption and repellent characeristics producedby theethersmake, them use;- 112 inheie and.celd..-settin gz glues. They have. een'..ound1a1so-toact. as mild. curing agents: for

v various. synthetic rubbers; and also; addtacktoi ndrefleetthermilling of rsuchmaterials.

In order to effect: rapid-cure of the claimed ethers; of tri-(hydmxymethyliphenol, catalysts usually.- added; Acids or acid engendering reagents. have been. found 'most. satisfactory. Where the ether group is unsaturated, sulphur and rubberaccelerators, as well as metallic-driers, alieieflective. 01Ev the acid type. phosphoric acid has; been; found most. suitable. but other acids such; hydrochloric, maleic,.oxa-lic, etc., can be LSC L Aipai'ticularly suitable class of catalysts are-the ammonia an amine salts of sulphuric or sulphonic acids; e. .g ammoniumsalts of. p-toluene sulfonic. acid; pephenol sulfonic acid, o-phenol sulfonic acid; the-morpholine salts of '1)- and/or o-phenol' ulphonic. acid, of benzene sulfonic acid; ethyl hydrogensulphate; the ureasa'l-tof ortho and/or para phenol sulfonic acid. of p-toluene sulfonic acid; the mono urea, morpholine and ethanolamine salts of sulphuric acid.

This class of catalysts has several advantages. They are readily soluble in the ethers of tris- (hydroxymethyhphenol and varnishes prepared fron suchethers. The-acid natureof the catalystis modified so that corrosion ofmetalliccontainerszand premature. gelation of varnishes duringstorageis greatly reduced. An entirely unex-- pectedadvantage derived from the use of this. class ofcatalysts is gloss retention in pigmented; films, For example, the addition of several per cent of phosphoric acid to apaint, based on the, allyl ether of tri-(hydroxy me thyl) phenol and. pigmented with T102, will cause the paint to lose its gloss when bakedto effect cure. However,

several per cent of saltssuch as those derived frominorpholine or urea and pand/or o-phenol sulionic-acid canbeadded to the paint without deteriorating the gloss of the. cured paint. Inmaniicasespthegloss of thecured film is actually.

improved over that of an uncatalyzed film by the.

additionof the catalyst.

Theethers have been found particularly useiulas modifiers for the various vinyl type resins, e. g polyyinyl alcohol, polyvinyl acetals (genera ieally. so; designated) which include polyvinyl.

formal, polyvinyl acetal, polyvinylbutyral. etc.. :65.515. obtained by the hydrolysis, of polyvinyl esterae. g., polyvinyl acetate, and then reacting; the hydrolyzed productwith the; appropriate al-.

ehydeiete. The use of these, others for this.

been found to be useful as plasticizers for various; 7k ing resjns;

"in this" connection, 1-allyloxy-2,4,6-tris(hy-- droxymethyDbenzene has been compounded with carbon black. After curing, the material was found to be unaffected when immersed in alkali solutions f .up to forty per cent which were allowed to boil to'dryness on its surface; While ethers of 2,4,6-tris(hydroxymethyl)- phenols have beenfound .to be very useful as plasticizers for. various-resins, they are rather expensive to produce in the pure state because of the separation process.. It has been found that for many applications the ethers of the tris(hydroxymethyl)phenols can tolerate cer-' tain amounts of the ethers of --2-(hydroxymethyl') phenol, 4- (hydroxymethyl) phenol, 2,6-bis- (hydroxymethyl) phenol and 2,4-bis(hydroxy-' methyl) phenol. It has been further found that the presence of theethers. of the uniand biscompounds does not detract appreciably from the beneficial results obtained so long as-the etherof the tris-compound is present in the major proportion of more. than fifty per cent by weight. It will, ofcourse, beapparent, mixtures of .these ethers, where the trimethylol phenol etherconstitutes less: than 50% of themixtures, are also contemplated. In general, if at least 2.5 mols of formaldehyde are used to each molof phenol; .the major proportion of the reaction product willbe the tris(hydroxymethyl) compound. Consequently, the corresponding ether: mixture will predominate in the ether of the tris(hydroxymethyl) phenol. The formula of such mixtures may be represented as follows:

where, as pointed out previously, R represents'a'n unsaturated aliphatic radical and halogenated unsaturated aliphatic radicals, and n' is an in-' teger and is at least one but not more than three, and in which the compound in which n is equal to three is in the major proportion.

Examples illustrating the production of such mixtures of methylol phenol ethers are as follows, where all parts are by weight.

Example XIII Three hundred and fifty parts phenol and 900' parts 37.3% aqueous formaldehyde were mixed with stirring." To the solution was added 164 parts sodium hydroxide in 170 parts water and the whole reacted for six and one-half hours at 40 C. Analysis showed that 86.6 per cent of the formaldehyde had reacted to give about sixty per cent sodium tris(hydroxymethyl)- phenate along with the uniand bisthydroxymethyDphenates. Three hundred and three parts by weight of allyl chloride was added and the mixture reacted in a pressure reactor at 60 C. for three hours with vigorous stirring. Anal-- ysis showedthat 98.7 per cent of. theallyl .chloride reacted. The aqueous layer was drawn offand the organic-layer dehydrated by heatingunder a vacuum. The yield was 650 parts by weight of the allyl ethers of the mixed uni-, his

and tris(hydroxymethyl) phenols with the tris compound being present as the major component.

Example XIV hydroxide in 167 parts water were mixed and reacted .for sevenand one-half hours at 40 (Lat which time 83.5 per cent of the formaldehyde had reacted to give a major proportion of sodium tris(hydroxymethyl)phenate as the product. Allyl. chloride in the amount of 273 parts was added and the whole mass heated to 60 C. in. an air. tight reactor for three and one-half hours with vigorous'stirring. At the end of this period 93.1 per cent of the allyl chloride had reacted. The isolated organic layer was dehy drated to yield 625 parts of the allyl ethers of mixed uni-, bis-, and tris(hydroxymethyl)- phenol with the tris compound as the major component as a brown somewhat viscous oil.

The hydroxymethylphenyl ethers of this invention may also be condensed to produce a variety of resins in conjunction with such materials as resorcinol, cardinol, etc. By reacting the ethers with polybasic acids, e. g., succinic, phthalic, etc; alkyd-type resins are produced which are use-" ful in forming lacquers and films. They may also be used as curing agents for butadiene rubbers.

By reacting the tris-(hydroxymethyl)phenyl ethers with monohydric alcohols, substituted alcohols, such as ethanolamine or ethylene chlorohydrin, additional groups can be introduced into the molecule. v

The properties of the above-described methylol phenyljethers are believed to be unique for several reasons, among them being the monomeric form'of the ether. Because of the monomeric characteristics of these methylol phenyl ethers, it is possible to obtain a better compatibility with resins than is possible by the use of etherified resinous condensation products of phenol and formaldehyde. In addition, these methylol phenyl ethers appear to be more readily soluble and'dissolve more rapidly in a greater variety of solvents than etherified resinous materials. Moreover, the compositions herein claimed can be applied with spraying apparatus from solutions having much higher solids content than is possible with etherified phenolic resins. This permits substantial savings in the use of solvents and recovery thereof. Finally, the methylol phenyl ethers herein claimed have excellent shelf life, i.' e., they can be stored for long periods of time at normal temperatures without danger of change in the constitution of the material due,

for example, to condensation or polymerization of any reactive groups. The presence of the ether group aids substantially in maintaining the shelf life of the methylol phenyl ethers. However, the stability of the material at normal temperatures does not harm its ability to con"- dense rapidly when it is desired to do so by the application of higher temperatures, for example, from to 250 C.

What I claim as new and desire to secure by Letters Patent of the United States is:

.1. A composition of matter comprising a compound corresponding to the general formula HOCH CHIOH HzOH derivatives of the aforesaid unsaturated aliphatic 5 radicals. 1

2. A composition of matter comprisin a mixture of ingredients comprising (1) a compound represented by the general formula HOCH CHzOH HzOH where R represents a member of the class consisting of unsaturated aliphatic radicals containing at least three carbon atoms and halogenated derivatives of the aforesaid unsaturated aliphatic radicals and (2) compounds corresponding to the general formula where n represents one of the following: 1,2, and

where n is one of the following: 1,2.

5. 1 methallyloxy-2,4,6-tris(hydroxymethyl)- benzene.

6. 1 (2' chloroallyloxy) -2,4,6-tris(hydroxymethyl) benzene.

7. The method of preparing a compound corresponding to the general formula HOCHr- CHzOH HzOH where R represents a member of the class consisting of unsaturated aliphatic radicals containing at least three carbon atoms, and halogenated derivatives of said unsaturated aliphatic groups, which process comprises reacting (1) previously isolated metallic 2,4,6 tris(hydroxymethyl) phenate where the metal atom replacing the hydrogen of the phenolic OH is a member of the class selected from sodium and barium with (2) a halide having the general formula RX where R has the meaning given above and X is a halogen of the class consisting of chlorine, bromine and iodine at a temperature not exceeding substantially 65 C.

8. The method as in claim 7 where R is the allyl group.

9. The method of preparing 1-allyloxy-2,4,6- tris(hydroxymethyl) benzene which comprises reacting preformed sodium 2,4,6-tris(hydroxymethyl) phenate with allyl chloride at a temperature not exceedin substantially 65 C.

10. A heat-converted material obtained by heating at a temperature of from to 250 C. a composition comprising a compound corresponding to the general formula HOCH l CHIOH where R represents a member of the class consisting of unsaturated aliphatic radicals containing at least three carbon atoms, and halogenated derivatives of the aforesaid unsaturated aliphatic radicals.

11. A heat-converted material obtained by heating at a temperature of from 75 to 250 C. a mixture of ingredients comprising (1) a compound represented by the general formula HOCH CHIOH HzOH where R represents a member of the class consisting of unsaturated aliphatic radicals containing at least three carbon atoms and halogenated derivatives of the aforesaid unsaturated aliphatic radicals and (2) compounds corresponding to the general formula (CHzOHh Where n represents one of the following: 1, 2, and R has the meaning given above.

12. A heat-converted material obtained by heating a composition comprising l-allyloxy- 2,4,6-tris(hydroxymethyl)benzene at a temperature of from 75 to 250 C.

13. A heat-converted material obtained by heatin a composition comprising l-methallyloxy-2,4,6-tris(hydroxymethyl)benzene at a temperature of from 75 to 250 C.

14. A heat-converted material obtained by heatin a composition comprising l-(2-chloroallyloxy) -2,4,6-trisfhydroxymethyl)benzene at a temperature of from 75 to 250 C.

ROBERT W. MARTIN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,495,232 Drisch et a1 Jan. 24, 1950 2,558,688 Landa June 26, 1951 

7. THE METHOD OF PREPARING A COMPOUND CORRESPONDING TO THE GENERAL FORMULA
 10. A HEAT-CONVERTED MATERIAL OBTIAINED BY HEATING AT A TEMPERATURE OF FROM 75* TO 250* C. A COMPOSITION COMPRISING A COMPOUND CORRESPONDINT TO THE GENERAL FORMULA 